KR20190071747A - Process for producing BTX from a C5-C12 hydrocarbon mixture - Google Patents

Abstract

The present invention (i) providing a shaped article comprising a zeolite and a binder, the molded body is obtained by molding, firing and cooling, the zeolite has a silica of 25-75 (SiO ₂₎ to alumina (Al ₂ O ₃ ) ZSM-5 having a molar ratio; (ii) optionally drying the shaped body at a temperature of 100 to 300 DEG C for at least one hour; (iii) depositing a metal hydride on the shaped body by immersing the metal hydride in an amount of 0.010-0.30 wt% with respect to the entire catalyst for a period of 2 hours or less; (iv) optionally rinsing the shaped body on which the metal is deposited with water; And (v) heat treating the metal-deposited article in air at a temperature of 250-300 ° C for 1-5 hours, wherein the catalyst comprises less than 0.05% by weight sodium And cesium.

Description

Process for producing BTX from a C5-C12 hydrocarbon mixture

The present invention relates to a process for producing a hydrocracking catalyst. The present invention also relates to a process for preparing BTX from a mixed feed stream comprising C ₅ -C ₁₂ hydrocarbons by contacting said feed stream with said catalyst in the presence of hydrogen.

WO 02/44306 A1 and WO 2007/055488 A1 disclose a process for the preparation of mixed hydrocarbon feedstocks having a boiling point of 30-250 占 폚 in a mixture of aromatic hydrocarbon compounds and LPG (liquefied petroleum gas; C ₂ , C ₃ and C ₄ hydrocarbons) Lt; / RTI > Thus, a hydrocarbon feedstock with a boiling point and hydrogen of 30-250 占 폚 is introduced into a reaction zone wherein the hydrocarbon feedstock is hydrotreated and / or transalkylated in the presence of a catalyst such as BTX (Benzene, Toluene , and mixed Xylene (benzene, toluene, and mixed xylene), performing hydrogenolysis, recovering the aromatic hydrocarbon compound and LPG by gas-liquid separation and distillation, respectively, Non-aromatic hydrocarbon compound. The methods of WO 02/44306 A1 and WO 2007/055488 A1 are directed to BTX which makes it impossible to produce chemical grade BTX without solvent extraction and to a relatively large amount of non-aromatic hydrocarbons co-boiling And a relatively large amount of fuel gas p obtained by consuming the produced LPG.

US2009 / 0272672 are catalytic aromatization and then initiate the catalytic hydrogenation dealkylation process of the C ₄ -C ₁₀ aliphatic and cycloaliphatic products and mixed C ₈ -C ₁₄ alkyl-aromatic compound subjected to hydrogenation dealkylation reaction. In this process, the hydrocarbon is a platinum couple at a temperature of 2 to pressure and H2 / feed mole ratio of 3 to 6 in terms of the raw materials of 4 MPa of 400 to 650 ℃ - 5 to 100 of the modified by molybdenum couple SiO ₂ / Al < ₂ > O < _{3 &} gt ;.

US2006 / 0287564 describes a process for increasing the production of benzene from hydrocarbon mixtures, including separating the hydrocarbon feedstock from a hydrocarbon stream of C < ₆ > or less and a hydrocarbon stream of C < ₇ > The hydrocarbon stream below C ₆ is separated into a non-aromatic hydrocarbon stream and an aromatic hydrocarbon stream via a solvent extraction process. The C ₇ or higher hydrocarbon stream is fed to the reaction in the presence of a catalyst comprising platinum / tin or platinum / lead.

US3957821 describes a process for treating heavy reformates in which benzene and most lighter components are largely removed. The removed stream may contain a major portion of the benzene in the charge and may comprise a substantial portion of the toluene.

WO2013 / 182534 discloses a process for producing BTX from a C ₅ -C ₁₂ hydrocarbon mixture using a hydrocracking / hydrodesulphurisation (hydrodesulphurization) catalyst. According to WO2013 / 182534, the process produces a mixture substantially free of co-boilers of BTX, so that chemical grade BTX can be readily obtained.

WO2013182534 proposes a process for producing effluents which advantageously provide chemical grade BTX but which contain more of the desired components such as BTX and LPG and which contain lesser amounts of components such as methane .

US2004 / 082461 discloses a process for preparing a molecular sieve-binder extrudate which comprises the steps of: a) contacting a molecular sieve-binder extrudate with a corresponding aqueous solution of a Group VIII metal nitrate having a pH of 8 or less and determining the molar ratio of the Group VIII metal cation to the number of sorption sites in the extrudate Binder extrudate, and b) impregnating the molecular sieve-binder extrudate with a Group VIII metal by drying the molecular sieve-binder extrudate obtained in the step a), wherein the binder is essentially composed of alumina And no low-acid refractory oxides.

US2014 / 0316179 discloses a process for preparing a hydrocarbon aromatization catalyst. The process for preparing the formed catalyst may comprise: mixing the uncalcined Ge-ZSM-5 zeolite and the binder to form a mixture; Forming the mixture with the formed zeolite; Calcining the formed zeolite so as to contain no more than 0.1 weight percent residual carbon; Ion-exchanging the formed zeolite with cesium to make it non-acidic; Depositing platinum on the zeolite formed; And heating the formed zeolite to obtain a final catalyst; Wherein the final catalyst comprises 4.0-4.8 wt% cesium and 0.4-1.5 wt% platinum.

US2014 / 039233 discloses a catalyst composition suitable for converting an alkane having from 3 to 12 carbon atoms per molecule per molecule to an aromatic hydrocarbon, the catalyst composition comprising: MN / MA / Ga-zeolite, Represents one or more noble metals, and MA represents one or more alkali metals and / or alkaline earth metals. The MN / MA / Ga-zeolite is a zeolite comprising: 0.01 to 10% by weight of MN relative to the total of the MN / MA / Ga-zeolite; 0.01 to 10% by weight of MA for the entire MN / MA / Ga-zeolite; And 0.01 to 10% by weight of gallium (Ga) based on the total of the MN / MA / Ga-zeolite.

An unpublished, co-pending application PCT / EP2016 / 069554 discloses a process for producing BTX using a hydrocracking catalyst, said hydrocracking catalyst comprising a shaped body comprising a zeolite and a binder, And the amount of the hydrogenated metal is 0.01 to 0.3% by weight based on the entire catalyst, and the zeolite has a molar ratio of silica (SiO ₂ ) and alumina (Al ₂ O ₃ ) ZSM-5 < / RTI > This application discloses that such catalysts including ZSM-5 with a molar ratio of silica (SiO ₂ ) and alumina (Al ₂ O ₃ ) of 25 to 75 are sufficiently low in the Weight Hourly Space Velocity (WHSV) Ratio methane and substantially does not comprise a co-boiler of BTX.

International Patent Publication No. WO2017-032672 A1 (International Publication on Mar. 02, 2017)

The preparation of the hydrocracking catalyst may comprise the following multi-steps: providing a shaped body comprising zeolite and a binder, firing the formed body, and further drying the shaped body, Depositing the deposited metal, rinsing or rinsing the shaped body on which the hydrogenated metal is deposited, and heat treating it.

It would be desirable to provide a hydrocracking catalyst having the desired activity in an efficient manner by conserving time, energy and materials in one or more of the above steps.

It is an object of the present invention to provide a process for producing a hydrocracking catalyst and a process for converting a C ₅ -C ₁₂ hydrocarbon feed stream into a product stream comprising BTX which meets the above and / or other needs.

Thus, the present invention provides:

(i) providing a shaped body comprising a zeolite and a binder, wherein the shaped body is obtained by molding, firing and cooling, wherein the zeolite has a molar ratio of silica (SiO ₂ ) to alumina (Al ₂ O ₃ ) Lt; / RTI > is 25-75;

(ii) optionally drying said shaped body at 100-300 占 폚 for at least 1 hour;

(iii) depositing a metal hydride on the shaped body by impregnation for a period of 2 hours or less, so that the amount of the metal hydride is 0.010-0.30% by weight based on the catalyst;

(iv) optionally rinsing the shaped body on which the metal is deposited with water; And

(v) heat-treating the formed body on which the metal is deposited, at a temperature of 250-300 ° C in air for 1-5 hours;

Wherein the hydrogenation catalyst is produced by a method comprising the steps of:

The present invention also comprises a hydrocracking catalyst preparation step according to the process according to the invention, additionally comprising:

(a) providing a hydrocracked feed stream comprising C ₅ -C ₁₂ hydrocarbons;

(b) hydrocracking the feed stream in the presence of hydrogen, which include a temperature of 425-580 ℃, hourly space velocity of the pressure gauge and the 300-500kPa ^{3-30 h -1 (Weight Hourly Space Velocity} , WHSV) Contacting the hydrocracking catalyst formed by the process of any one of the preceding claims under process conditions to produce a hydrocracked product stream comprising BTX; And

(c) separating the BTX from the hydrocracking product stream;

≪ RTI ID = 0.0 > BTX < / RTI > production process.

The hydrocracking catalyst obtained by the process according to the present invention is used in a process for producing BTX according to the present invention and comprises a shaped body including a zeolite and a binder and a hydrogenated metal deposited on the shaped body, (ZSM-5) having a molar ratio of silica (SiO ₂ ) to alumina (Al ₂ O ₃ ) of 25 to 75, The zeolite of the shaped catalyst is in the hydrogen form.

The inventors have surprisingly found that high performance catalysts having a silica (SiO ₂ ) to alumina (Al ₂ O ₃ ) molar ratio of 25 to 75 generally omit some of the periods of time that were considered essential in the catalyst preparation process Can be produced in an extremely efficient manner.

In the prior art it has been considered essential to pre-dry the shaped body comprising the zeolite and the binder before the deposition of the hydrogenation catalyst. It has been found that such pre-drying is not necessary for the shaped bodies according to the invention to provide the desired catalytic performance.

The formed body is subjected to a step of impregnating the formed body to deposit the hydrogenated metal. Surprisingly, it has been found that the duration of impregnation can be significantly reduced - for example, to a duration of up to 2 hours to provide the desired catalytic performance. Typically, the impregnation duration according to conventional processes was about 24 hours at a temperature of about 60 占 폚.

In addition, it has been found that the step of rinsing or rinsing the molded article with the metal deposited thereon can be omitted. Here, the terms " rinsing " and " washing " The rinsing or washing step according to the conventional process required a large amount of DI water, thereby omitting such a process, thereby saving costs. The product obtained is then calcined and is also carried out for a short time - for example up to 5 hours. Typically, the firing duration according to conventional processes was 20 to 24 hours.

The process according to the invention therefore provides a catalyst in a very short time compared to methods known in the art and also provides a catalyst with the desired catalytic performance.

The process according to the present invention using the catalyst produces a hydrocracked product stream comprising BTX with a low methane content at high hourly space velocity (WHSV) and substantially no co-boilers. The low methane ratio means that more valuable components such as C ₂ -C ₄ hydrocarbons and BTX are present in the hydrocracked product stream. The absence of an azeotrope material in the BTX allows the chemical grade BTX to be obtained by simple distillation of the product stream. This can be achieved by a relatively high level of WHSV, which means that the intended product can be obtained at a higher rate requiring a small amount of reactor, resulting in lower capital expenditure (CAPEX).

The term " C _n hydrocarbons " (where n is a positive integer) as used herein refers to all hydrocarbons having n carbon atoms. Moreover, the term " C _{n +} hydrocarbons " refers to all hydrocarbon molecules having n or more carbon atoms. Thus, the term " _{C5 +} hydrocarbon " refers to a mixture of hydrocarbons having five or more carbon atoms.

a) Step

According to step a) of the process according to the invention, a hydrocracked feed stream comprising C ₅ -C ₁₂ hydrocarbons is provided.

Hydrocracking feed stream

The hydrocracked feed stream used in the process of the present invention is a mixture comprising C ₅ -C ₁₂ hydrocarbons and preferably has a boiling point in the range of 30-195 ° C. Preferably, the hydrocracked feed stream comprises mainly C ₆ -C ₈ hydrocarbons.

The hydrocracked feed stream can be provided by feeding a fresh feed stream and optionally mixing it with another stream-such as the hydrocracked product stream, for example, a stream re-used from toluene as needed. Mixing with other streams is optional. If, for example, mixing with the re-use stream does not occur, the hydrocracked feed stream is the same as the fresh feed stream. Suitable examples of fresh feed streams include first stage or multistage water-treated pyrolysis gasoline, straight run naphtha, hydrocracked gasoline, light coker naphtha, and coke oven light but are not limited to, hydrogenation, enrichment, and / or depentanization of mono-aromatic compounds, including, but not limited to, oil, FCC gasoline, reformate or mixtures thereof. It goes through.

For example, a typical composition of the first stage water-treated pyrolysis gasoline comprises 10 to 15 wt% C ₅ olefin, 2 to 4 wt% C ₅ paraffins and cycloparaffins, 3 to 6 wt% C ₆ olefin, 1 to 3% of C ₆ paraffins and naphthenes (naphthenes) by weight, 25 to 30% by weight of benzene, 15 to 20% toluene by weight, from 2 to ethylbenzene 5% by weight, 3% to 6% by weight By weight of xylene, 1 to 3% by weight of trimethylbenzene, 4 to 8% by weight of dicyclopentadiene and 10 to 15% by weight of C ₉₊ aromatics, alkylstyrenes and indenes indenes (see Table E3.1 of "Applied Heterogeneous Catalysis: Design, Manufacture, and Use of Solid Catalysts" (1987) JF Le Page).

It is preferred that the non-aromatics contained in the hydrocracked feed stream are saturated to reduce exotherms in the catalyst bed comprising the hydrocracking catalyst used in the present process. Thus, preferably, the fresh feed stream is a hydrogenated stream. The hydrogenation advantageously has further hydrodesulfurization function. This is advantageous in that the fresh feed stream has a low sulfur content. The low sulfur content in the fresh feed stream has the advantage that the hydrocracking catalyst does not need to have a hydrodesulphurization function.

The fresh feed stream or hydrocracked feed stream used in the process of the present invention may contain up to 300 wppm sulfur (i.e., the weight of sulfur atoms present in any compound relative to the total weight of the feed).

In some embodiments, the fresh feed stream used in the process of the present invention is a stream that is treated to be enriched in mono-aromatics. The term " mono-aromatic compound " as used herein means a hydrocarbon having only one aromatic ring. Suitable means and methods for concentrating the content of mono-aromatics in the mixed hydrocarbon stream are well known in the art such as, for example, the Maxene process (see Bhirud (2002) Proceedings of the DGMK-conference 115-122) .

In some embodiments, the fresh feed stream used in the process of the present invention is depentanized. Preferably, the fresh feed stream comprises not more than 5% C ₅ hydrocarbons, more preferably not more than 4%, not more than 3%, not more than 2%, or not more than 1% by weight of hydrocarbons.

Preferably, the hydrocracked feed stream is provided by a process that does not include a benzene removal step or a C ₆ hydrocarbon removal step. This means that the intentional removal of benzene is not carried out in the step of providing the hydrocracking feed stream or the fresh feed stream. According to the present invention, the benzene azeotropes present in the hydrocracked feed stream are advantageously converted to useful LPG.

Preferably, the hydrocracked feed stream comprises at least 10 wt% benzene, e.g., at least 20 wt% benzene, at least 30 wt% benzene or at least 40 wt% benzene, and / or up to 90 wt% Benzene, for example at least 80% by weight, at least 70% by weight, at least 60% by weight, or at least 50% by weight of benzene.

Preferably, the fresh feed stream comprises at least 10 wt% benzene, such as at least 20 wt% benzene, at least 30 wt% benzene, or at least 40 wt% benzene, and / or up to 90 wt% Benzene, such as up to 80 wt.%, Up to 70 wt.%, Up to 60 wt.%, Or up to 50 wt.% Of benzene.

b) Step

According to step b) of the process according to the invention, the hydrocracked feed stream is contacted with the hydrocracking catalyst prepared according to the process of the present invention in the presence of hydrogen in a hydrocracking reactor.

The products (hydrocracking product streams) produced by the hydrocracking step of the process of the present invention include LPG, BTX, and methane.

The term " LPG " as used herein means a well-known acronym for " liquefied petroleum gas ". LPG generally consists of a mixture of C ₂ -C ₄ hydrocarbons, for example a mixture of C ₂ , C ₃ and C ₄ hydrocarbons.

The term " BTX " is well known in the art and refers to a mixture of benzene, toluene and xylene.

The term " chemical grade BTX " as used herein means a hydrocarbon mixture comprising less than 5% by weight of hydrocarbons, excluding benzene, toluene and xylene, preferably less than 4% by weight of benzene, By weight of hydrocarbons other than xylene, more preferably less than 3% by weight of hydrocarbons other than benzene, toluene and xylene, most preferably less than 2.5% by weight of hydrocarbons other than benzene, toluene and xylene.

Also, " Chemical Grade BTX " produced by the process of the present invention comprises less than 1 wt% non-aromatic C ₆₊ hydrocarbons, preferably less than 0.7 wt% non-aromatic C ₆₊ hydrocarbons, Preferably 0.5% by weight of non-aromatic C ₆₊ hydrocarbons, and most preferably less than 0.2% by weight of non-aromatic C ₆₊ hydrocarbons. The most important contaminants are non-aromatic compounds with boiling points close to benzene, such as methylcyclopentane, n-hexane, 2-methylpentane and 3- methylpentane), but are not limited thereto. The most important non-aromatic compounds with boiling points close to toluene are 2,4-dimethylpentane, 3,3-dimethylpentane, and 2,2-dimethylpentane (2 , 2-dimethylpentane).

Thus, the hydrocracking product stream is substantially free of non-aromatic C _{6 +} hydrocarbons. As meant herein, the term "substantially non hydrogenolysis product stream - there is no aromatic C ₆₊ hydrocarbons (hydrocracking product stream substantially free from non -aromatic C 6+ hydrocarbons)" is not the above-described hydrocracking product stream 1 Aromatic C ₆₊ hydrocarbons, preferably less than 0.7% by weight of non-aromatic C ₆₊ hydrocarbons, more preferably 0.5% by weight of non-aromatic C ₆₊ hydrocarbons, And most preferably less than 0.2% by weight of non-aromatic C ₆₊ hydrocarbons.

The term " aromatic hydrocarbons " is well known in the art. Thus, the term " aromatic hydrocarbon " refers to stable cyclic conjugated hydrocarbons (by discretion) and this compound has significant stability over, for example, virtually parasitic structures according to the Kecula structure. The best known measure of aromatics for a given hydrocarbon is that the most common method for determining the aromaticity of a given hydrocarbon is the observation of the diatropicity in the 1 H NMR spectrum such as the chemical shift of the benzene ring protons in the range of 7.2 to 7.3 ppm Existence.

The hydrocracked product stream produced in the process of the present invention preferably contains less than 5% by weight of methane. Preferably the hydrocracking product stream produced in the process of the present invention comprises less than 4% by weight methane, more preferably less than 3% by weight methane, more preferably less than 2% by weight methane, More preferably less than 1.4 wt.% Methane, more preferably less than 1.3 wt.% Methane, more preferably less than 1.2 wt.% Methane, more preferably less than 1.5 wt.% Methane, more preferably less than 1.4 wt. Less than 1.1 weight percent methane, and most preferably less than 1 weight percent methane.

Preferably, the hydrocracking product stream also does not substantially contain C ₅ hydrocarbons. Such as by means herein, the term "hydrocracking product stream substantially contains no C ₅ hydrocarbons (hydrocracking product stream substantially free from C ₅ hydrocarbons)" is not of the above-described hydrocracking product stream is less than 1% by weight C ₅ Means that it comprises hydrocarbons and preferably comprises less than 0.7 wt% C ₅ hydrocarbons, more preferably less than 0.6 wt% C ₅ hydrocarbons, and most preferably less than 0.5 wt% C ₅ hydrocarbons do.

A particular advantage of the process according to the invention is that the hydrocracking product stream does not contain substantially non-aromatic C _{6 +} hydrocarbons because these hydrocarbons typically have a boiling point close to the boiling point of the C ₆₊ aromatic hydrocarbons . Therefore, the non-The separation by distillation from the aromatic C ₆₊ hydrocarbons contained in the hydrocracked product stream of an aromatic C ₆₊ hydrocarbons can be difficult.

Process conditions

The process conditions under which the hydrocracking of the feed stream is effected is an important factor in determining the composition of the hydrocracked product stream.

In general, if the space velocity is too high, it may not be possible to obtain the chemical grate BTX by simple distillation of the product stream, because not all BTX azeotrope materials are hydrogenated. However, at a too low space velocity, the yield of methane increases and the amount of propane and butane produced decreases. Also, the high space velocity requires a smaller reactor volume and therefore requires less CAPEX. It is therefore advantageous to carry out the process of the present invention at a high space velocity such that substantially all azeotrope materials of BTX can be hydrocracked.

It has been found that the hydrocracking step (b) is advantageously carried out at a high space velocity such that substantially all of the BTX azeotrope materials can be hydrocracked because of the high activity of the catalyst. In the catalyst used in the process of the present invention, without being bound by theory, the hydrogenated metal and the zeolite are converted into a shorter diffusion length between two positions in close proximity to each other. This allows the BTX azeotrope material to be hydrocracked at a high rate.

Thus, in some preferred embodiments, step (b) is performed at a WHSV of 3 to 30 h ^-1 , for example at least 5 h ^-1 , at least 6 h ^-1 , At least 7 h- ¹ , at least 8 h- ¹ , and / or 25 h- ¹ Less than or equal to 20 h ^-1, less than or equal to 15 h ^{-1, and} less than or equal to 10 h ^-1 . The high WHSV allows a particularly low reactor volume and low CAPEX.

It has also been found that step (b) can be operated at relatively low temperatures. This allows greater operating flexibility as well as lower thermal duty and allows longer cycle lengths. Thus, in some preferred embodiments, step (b) is performed at a temperature of 425 to 445 ° C. In another embodiment, step (b) is carried out at a temperature of 450 to 580 캜. Higher temperature ranges lead to higher hydrocracking conversion.

The hydrocracking of the feed stream is preferably carried out at a pressure of 300 to 5000 kPa gauge, more preferably at a pressure of 600 to 3000 kPa gauge, particularly preferably at a pressure of 1000 to 2000 kPa gauge, kPa gauge pressure. Increasing the pressure in the reactor can increase the conversion of C ₅₊ non-aromatics, but the higher the pressure, the higher the yield of methane and the greater the rate of hydrogenation to the cyclohexane species, where the aromatic rings are susceptible to decomposition into LPG species. This reduces the aromatic yield as the pressure increases, and since the cyclohexane and its isomer, methylcyclopentane, are not completely hydrocracked, the pressure of 1200-1600 kPa can result in high purity of the resulting benzene.

The hydrocracking step is carried out in the presence of excess hydrogen in the reaction mixture. This means that there is more stoichiometrically more hydrogen in the reaction mixture undergoing hydrocracking. Preferably, the molar ratio of hydrogen to hydrocarbon species in the reactor feed (H ₂ / HC molar ratio) is from 1: 1 to 4: 1, preferably from 1: 1 to 3: 1, most preferably from 2: : 1. Higher benzene purity in the product stream can be obtained by selecting a relatively low H ₂ / HC mole ratio. The term " hydrocarbon species " in this context means all hydrocarbon molecules present in the reactor feed such as benzene, toluene, hexane, cyclohexane, and the like. Next, we need to know the composition of the feed to calculate the average molecular weight of this stream so that we can calculate the correct hydrogen feed rate. Excessive hydrogen in the reaction mixture inhibits coke formation believed to cause catalyst deactivation.

catalyst

The catalyst used in the process of the present invention is produced by the above-described process of the present invention.

There is provided a molded article comprising a zeolite and a binder in step (i) of the hydrocracking catalyst production method, wherein the zeolite is ZSM-5 having a molar ratio of silica (SiO ₂ ) to alumina (Al ₂ O ₃ ) of 25 to 75 . The shaped body is formed by shaping the zeolite and the binder into a desired shape, for example extrusion, and calcining it in the air, for example at a temperature of 400 to 600 ° C for 1 to 16 hours, Followed by cooling to room temperature. Molded articles obtained by such molding (extrusion) and subsequent firing and cooling are commercially available. The shaped body is stored until further use.

The molded article stored at room temperature may be subjected to a drying step (ii) for drying the molded article at a temperature of 100 to 300 DEG C for at least one hour before step (iii). When the step (ii) is carried out, the drying is preferably carried out at 200 to 300 ° C for 1 to 2 hours. Preferably, however, the process according to the invention does not involve step (ii), i.e. step (iii) is carried out without heat treatment (reaching 100 캜) after step (i).

In step (iii), the shaped body is wet impregnated to deposit the hydrogenated metal on the shaped body. The impregnation is carried out for a time of 2 hours or less, for example 0.5 to 2 hours or 0.5 to 1.5 hours, which is significantly shorter than the conventional process. Impregnation can even be carried out at room temperature, leading to cost reduction.

The shaped body stored with the deposited hydrogenated metal may undergo a step (iv) of rinsing or washing prior to step (v). The rinsing can be performed with a large amount of water, but may also be performed by placing the shaped body in a container having a relatively small amount of water (e.g., five times the volume of the shaped body). Preferably, however, the method according to the invention does not comprise step (iv).

In step (v), the shaped body stored with the deposited hydrogenated metal is heat treated in air for a short time, i.e., 1 to 5 hours. The temperature is 250 to 300 캜, preferably 270 to 290 캜. Preferably, the heat treatment is carried out at a temperature of 270 to 290 DEG C for 1 to 3 hours.

In a particularly preferred embodiment of the present invention, the method according to the present invention does not include step (ii) and does not include step (iv).

The hydrocracking catalyst used in the process of the present invention comprises a shaped body comprising a metal hydride and ZSM-5 zeolite and a binder, wherein the metal hydride is deposited on the shaped body. Examples of such shaped bodies include, but are not limited to, spherical or cylindrical pellets, tablets, particles and extrudates. The shaped bodies typically have an average diameter of from about 0.1 mm to about 15 mm, for example from about 1 mm to about 7 mm, typically from about 1.4 mm to 3.5 mm. The diameter is generally measured with a slide caliper. The shaped bodies typically have an average length of 3 to 8 mm. As used herein, the average is an arithmetic average. One specific example of the shaped body is a cylindrical extrudate having an average diameter of about 1.6 mm (1/16 inch) and an average length of the extrudate of about 3 to 8 mm. In such a catalyst, the distance between the hydrogenated metal and the zeolite acid site is less than the distance in the mixed catalyst of the shaped zeolite body and the hydrogenated metal supported on the binder. The latter example would be a mixture of extrudates of ZSM-5 zeolite and Pt deposited on the shaped Al ₂ O ₃ phase.

In addition, the process of the present invention has been observed to obtain the desired LPG composition in the hydrocracked product stream. LPGs rich in C ₂ hydrocarbons can generally be more valuable than LPGs rich in C ₃ hydrocarbons. The hydrogenolysis catalyst used in the present invention if the hydrocracking feed stream is naphtha ZSM-5 zeolite extrudate, and compared to other hydrocracking catalysts comprising a mixture of a hydrogenated metal deposited on the formed binder higher C ₂ To C ₃ ratio.

Zeolites are well-defined channels, pores, and molecular sieves with cavities with well-defined pore sizes. As used herein, the term "zeolite" or "aluminosilicate zeolite" refers to an aluminosilicate molecular sieve. An overview of these properties can be found in, for example, Kirk-Othmer Encyclopedia of Chemical Technology, Volume 16, p. 811-853, chapter on molecular sieves and in Atlas of Zeolite Framework Types, 5th edition, ). The ZSM-5 zeolite is a mesoporous zeolite having a pore size of about 5-6 ANGSTROM. ZSM-5 zeolite is 10 and each ring zeolite, i.e., pores of 10 [SiO _4] and [AlO _4] ^- made of a tetrahedron. ZSM-5 zeolite is a zeolite having an MFI structure. The negative charge generated in [AlO ₄ ] ^- is neutralized by the cations in the zeolite.

The molar ratio of silica (SiO ₂ ) to alumina (Al ₂ O ₃ ) of the ZSM-5 zeolite is in the range of 25 to 75.

The use of zeolites with SiO ₂ to Al ₂ O ₃ molar ratios of 25 to 75 allows measurement of methane in the active (measured by WHSV), benzene and total aromatic contents (BTX, ethylbenzene (EB) and heavies) And exhibits the best catalytic activity obtained. Means and methods for quantifying the SiO ₂ to Al ₂ O ₃ molar ratio of zeolites are well known in the art and include atomic absorption spectrometer (AAS), inductively coupled plasma spectrometry (ICP) analysis, or XRF , But is not limited thereto. It should be noted that the SiO ₂ to Al ₂ O ₃ molar ratio referred to herein means the ratio in the zeolite before mixing with the binder for forming the molded body. Preferably, the SiO ₂ to Al ₂ O ₃ molar ratio is measured by XRF.

Preferably, the silica to alumina ratio of the ZSM-5 zeolite ranges from 30 to 65, more preferably from 35 to 60, and even more preferably from 40 to 55. In this ratio, in particular a silica to alumina ratio of at least 35, the best balance of achievable WHSV for the total aromatics and methane content in the hydrocracked product stream and the desired benzene purity is obtained.

The zeolite is in the form of a hydrogen form, i.e. having at least a portion of the original cation replaced by H + ions. Methods for converting aluminosilicate zeolites to hydrogen form are well known in the art. The first method involves direct treatment with an acid such as mineral acid (HNO ₃ , HCl, etc.). The second method is direct exchange with ammonium salts (eg NH ₄ NO ₃ ) followed by calcination.

Since the zeolite is in the form of hydrogen, no base exchange has taken place. For example, zeolite is not a basic ion that is exchanged with sodium or cesium, and is preferably not a basic ion that is exchanged with an alkali or alkaline earth metal (e.g., Group IA and Group IIA of the Periodic Table). The catalyst may comprise less than 0.05 wt.% Total sodium and cesium, preferably less than 0.04 wt.%, Or less than 0.01 wt.%, Based on the total weight of the catalyst. The catalyst of the present invention may comprise less than 0.05% by weight of total alkali and alkaline earth metals, preferably less than 0.04% or less than 0.01% by weight, based on the total weight of the catalyst. Preferably, no alkali or alkaline earth metal is added to the zeolite.

The catalyst used in the process of the present invention comprises 0.010 to 0.30% by weight, preferably 0.010 to 0.15% by weight of hydrogenation metal. In the context of the present invention, the term "% by weight" relates to the weight percent of the metal relative to the total weight of the metal hydride, zeolite and binder. The amount of hydrogenated metal in the catalyst is determined, for example, by performing XRF on the catalyst.

Preferably, the catalyst comprises from 0.015 to 0.095% by weight of hydrogenated metal. Catalysts containing hydrogenation metals in this range have been found to have particularly high benzene yields. Even more preferably, the catalyst comprises from 0.020 to 0.090 wt.%, From 0.035 to 0.080 wt.%, Or from 0.040 to 0.075 wt.% Of the hydrogenation metal. In this range, the amount of benzene lost by the process of the present invention (the amount of benzene in the hydrocracked product stream relative to the hydrocracked feed stream) and the amount of methane in the hydrocracked product stream are particularly low. The amount of total aromatics (BTX, ethylbenzene (EB) and heavy materials) in the hydrocracked product stream stream is particularly high.

Preferably, the metal hydride is at least one element selected from Group 10 of the Periodic Table of the Elements or rhodium or iridium. Preferred Group 10 elements are palladium and platinum, especially platinum.

The hydrocracking catalyst used in the process of the present invention should have sufficient hydrogenation activity. Therefore, it is preferable that the catalyst does not contain a secondary metal such as tin, lead or bismuth which inhibits the hydrogenation activity of the hydrogenated metal. Preferably, the hydrocracking catalyst used in the process of the present invention comprises 0.01 part by weight of tin, 0.02 part by weight of lead and 0.01 part by weight of bismuth (based on 100 parts by weight of the total catalyst weight), preferably 0.005 part by weight of tin, 0.01 part by weight and 0.005 part by weight of bismuth (based on 100 parts by weight of the catalyst total weight).

Also preferably, the hydrocracking catalyst used in the process of the present invention thus comprises less than 0.01 part by weight of molybdenum (based on 100 parts by weight of the total weight of the catalyst).

The hydrocracking catalyst comprises a shaped body comprising ZSM-5 zeolite and a binder. The metal hydride is deposited on the formed body. The presence of the binder in the shaped body gives the catalyst adequate crush strength to withstand the pressure in the larger reactor.

The binder material may be an inorganic oxide material. The binder material may comprise aluminum or silicon containing materials such as silica, alumina, clay, aluminum phosphate, silica-alumina, or combinations comprising at least one of the foregoing. Alumina (Al ₂ O ₃ ) is the preferred binder. The catalyst may comprise 99 wt.%, For example 1 to 99 wt.%, For example 10 to 50 wt.% Or 20 to 40 wt.% Of binder material, based on the total weight of the catalyst.

c) Step

The hydrocracking product stream comprises methane, LPG, BTX. The term " LPG " as used herein is a well known acronym for the term " liquefied petroleum gas ". LPG generally consists of a mixture of C ₂ -C ₄ hydrocarbons such as, for example, C ₂ , C ₃ , and C ₄ hydrocarbons. The process includes (c) separating BTX from the hydrocracked product stream. Step (c) may also comprise separating the LPG from the hydrocracking product stream. Wherein the hydrocracking product stream comprises methane and unreacted hydrogen contained in the hydrocracking product stream as a first separation stream, LPG contained in the hydrocracking product stream as a second separation stream, BTX as a third separation stream Can be separated by standard means and methods suitable for separation. Preferably, the BTX-containing stream is separated from the hydrocracking product stream by gas-liquid separation or distillation. The benzene may additionally be separated from the stream comprising BTX.

One non-limiting example of such a separation process of the hydrocracked product stream comprises a series of distillation stages. The first distillation step at a suitable temperature separates most of the aromatic species (liquid product) from hydrogen, H ₂ S, methane and LPG species. The gaseous stream from this distillation is further cooled (to about -30 캜) and distilled again to separate the remaining aromatic species and most of the propane and butane. The gaseous products (mainly hydrogen, H ₂ S, methane and ethane) are further cooled (to about -100 ° C.) to separate the ethane and leave hydrogen, H ₂ S and methane in the gas stream, Will be reused in. This reused gas stream portion is removed as purge from the system to regulate the level of H ₂ S and methane in the reactor feed. The amount of material removed depends on the level of methane and H ₂ S in the re-use stream, which in turn depends on the composition of the feed. The purging may be carried out (e.g. via a pressure swing adsorption device) to separate the high purity hydrogen stream and the methane / H ₂ S stream suitable for use as a fuel gas or as a fuel gas because it primarily contains hydrogen and methane, Can be processed.

In another embodiment, the present invention is directed to a process for producing benzene from a feed stream comprising C ₅ -C ₁₂ hydrocarbons, wherein the process described above comprises a hydrodealkylation product stream comprising benzene and a fuel gas (Or only the toluene and xylene fraction of the resulting BTX described above) with hydrogen under conditions suitable to produce the BTX of the present invention.

Suitable conditions for producing a hydrogenated dealkylation product stream comprising benzene and a fuel gas are well known and are described in detail, for example, in WO2013 / 182534, which is incorporated herein by reference.

Processes for hydrodealkylation of hydrocarbon mixtures containing C ₆ -C ₉ aromatic hydrocarbons include thermal hydrodealkylation and catalytic hydrogenation dealkylation (see, for example, WO 2010/102712 A2). Catalytic hydrodealkylation is preferred in the context of the present invention because such hydrodealkylation processes generally have a higher selectivity towards benzene than thermal hydrogenated dealkylation reactions. Preferably, a catalytic hydrogenated dealkylation reaction is used, wherein the hydrogenated dealkylation catalyst comprises a supported chromium oxide catalyst, a supported molybdenum oxide catalyst, platinum on silica or alumina, and platinum oxide on silica or alumina .

The above process conditions useful for hydrodealkylation are described herein as " hydrogenated dealkylation conditions ", and can be readily determined by one of ordinary skill in the art. The process conditions used for the thermal hydrogenated dealkylation are described, for example, in DE 1668719 A1 and include a temperature of 600 to 800 ° C, a pressure of 3 to 10 MPa gauge and a reaction time of 15 to 45 seconds. The process conditions used for the preferred catalytic hydrogenated dealkylation preferably include temperatures of 500 to 650 ° C, 3.5 to 7 MPa gauge pressure and 0.5 to 2 h ^-1 WHSV (Commercial Catalysts: Heterogeneous Catalysts ed Howard F. Rase (2000) loc.

The hydrodealkylated product stream is typically separated into a liquid stream (containing benzene and other aromatic species) and a gas stream (containing hydrogen, H ₂ S, methane and other low boiling point hydrocarbons) by a combination of cooling and distillation . The liquid stream is further separated into a benzene stream, a C ₇ to C ₉ stream and a heavy aromatic stream by distillation. The C ₇ to C ₉ stream, or a portion thereof, is fed back to the reactor section and reused to improve overall conversion and benzene yield. Said heavy aromatic stream comprising polyaromatic species such as biphenyl is preferably not reused in said reactor and is exported to a separated product stream. The gaseous stream contains a large amount of hydrogen and can be reused via the reuse gas compressor to the reactor section. It can be used to re-adjust the gas concentration of the expanded methane and H ₂ S in the reactor charge.

While the invention has been described in detail for the purpose of illustration, it is to be understood that such detail is solely for the purpose of illustration and that modifications may be made by those skilled in the art without departing from the spirit and scope of the invention as defined in the claims.

Furthermore, the present invention is directed to all possible combinations of features described herein, particularly those combinations that are present in the claims. Thus, any combination of features associated with the composition according to the invention; All combinations of features associated with the process according to the present invention and any combination of features associated with the composition according to the present invention and features associated with the process according to the present invention are described herein.

It should also be noted that the term " comprising " does not exclude the presence of other configurations. However, it should be understood that the description of a product / composition comprising specific ingredients also discloses a product / composition consisting of these components. Products / compositions composed of these components may be advantageous in that they provide a simpler and more economical way for the manufacture of the product / composition. Similarly, it should be understood that the description of a process including specific steps also discloses a process comprising these steps. The process consisting of these steps may be advantageous in that it provides a simpler and more economical process.

Hereinafter, the present invention will be described by the following examples, but the present invention is not limited thereto.

Example of catalyst synthesis

In the examples described herein, "zeolite extrudate" refers to ZSM-5 zeolite powder (CBV 5524GCY (1.6) from Zeolyst International), which has a molar ratio of silica (SiO ₂ ) to alumina (Al ₂ O ₃ ) of about 50 By weight of ZSM-5 zeolite powder and about 20% by weight of Al ₂ O ₃ as a binder. The resulting extrudate is produced by extrusion and subsequent heat treatment and cooling. The resulting ZSM-5 extrudate is H-form and contains less than 0.05% by weight Na ₂ O.

Preparation of Comparative Catalyst

Comparative Catalyst A

The resulting 100-fold ZSM-5 extrudate was dried in air at 150 < 0 > C overnight (15 hours) and cooled to room temperature in a desiccator.

82.1 g of a 0.005 MH ₂ PtCl _{6 6} H ₂ O aqueous solution was diluted in a flask with 205 g of deionized water and then heated to 60 ° C. 100 g of the pre-dried ZSM-5 extrudate was added to the solution and the flask was covered. The extrudate was slowly stirred in the solution at 60 占 폚 for 24 hours (using a magnetic stirrer), and then the liquid was drained.

The extrudate was rinsed with large amounts of water (5 L). Further, the extrudate was washed by stirring with 1 L of water and separated.

The extrudate was heated to 90 DEG C (2 DEG C / min) at room temperature, held at 90 DEG C for 15 hours, heated at 90 DEG C to 280 DEG C (3 DEG C / min) . A number of catalyst samples were prepared using the methods described above, and the Pt content and catalyst performance data were averaged and shown in Table 2.

Example Catalyst B. Reduction in (iii) impregnation, (iv) cleaning and (v) heat treatment

10 g of the extrudate were dried in air at 300 DEG C for 2 hours (from room temperature to 300 DEG C at 2 DEG C / min) and the cooled extrudate was used immediately after cooling.

8.21 g of 0.005 MH ₂ PtCl ₆ .6H ₂ O aqueous solution was diluted with 20.5 g of deionized water. 10 g of the pre-dried ZSM-5 extrudate was added to the solution at room temperature and the flask was covered. The extrudate was slowly stirred in the solution at ambient temperature for 1 hour (using a magnetic stirrer) and the liquid was drained off.

The extrudate was then placed in a funnel filled with 50 ml water and the water was dropped at a controlled rate (100 ml / h).

The extrudate was heated at a temperature of 90 ° C at a rate of 2 ° C / min, maintained at 90 ° C for 3 hours, heated at 90 ° C to 280 ° C at a rate of 3 ° C / min, .

Examples Catalyst C. Reduction in (ii) drying, (iii) impregnation, (iv) scratch and (v) heat treatment

The extrudate was used without prior drying.

8.21 g of an aqueous solution of 0.005 MH ₂ PtCl ₆ .6H ₂ O was diluted with 20.5 g of deionized water in a flask and the temperature was raised to 60 ° C. 10 g of the obtained ZSM-5 extrudate was added to the solution and the flask was covered. The extrudate was slowly stirred in the solution at ambient temperature for 1 hour (using a magnetic stirrer) and the liquid was drained. The extrudate was then placed in a funnel filled with 50 ml water and the water was dropped at a controlled rate (100 ml / h).

The extrudate was heated from 90 ° C to 90 ° C at room temperature, maintained at 90 ° C for 3 hours, heated again at 90 ° C to 280 ° C at 3 ° C / min and fired in the air for 2 hours.

Example Catalyst D. Reduction in (ii) drying, (iii) impregnation, (iv) cleaning and (v) heat treatment

The extrudate was used without prior drying.

0.005 MH ₂ PtCl ₆ .6H ₂ O) was diluted in a flask with 20.5 g of deionized water and then heated to 60 ° C. 10 g of the obtained ZSM-5 extrudate was added to the solution and the flask was covered. The extrudate was slowly stirred in the solution at ambient temperature for 1 hour (using a magnetic stirrer) and the liquid was drained. The extrudate was heated from room temperature to 90 DEG C at 2 DEG C / min, held at 90 DEG C for 3 hours, heated from 90 DEG C to 280 DEG C at 3 DEG C / min, and fired in the air for 2 hours.

[Savings in steps (ii) to (v) of comparison catalyst] catalyst (ii) drying (iii) Impregnation (iv) (v) heat treatment B Energy, time Substance (water), time Energy, time C Energy, time Energy, time Substance (water), time Energy, time D Energy, time Energy, time Substance (water), time Energy, time

Catalyst test

Referring to Examples 1 to 4, the catalysts described in this application were tested for hydrocracking using a stainless steel tube reactor as described below. 0.10 g of catalyst (20-40 mesh size) was premixed with 30 grit of SiC and diluted to 3 ml and loaded into the reactor.

Reactor Description: 1/4 "inch tube, 0.028" wall thickness. 1/16 "thermocouple with 1/8" spacer bar; 12 "x 1" brass over sleeve; The reactor bed is about 5-6 inches long from the center of the sleeve.

The pre-activation of the catalyst (drying, Pt reduction), the composition of the hydrocracked feed stream and the conditions in the reactor are described in Examples 1-4.

In all experiments, the WHSV was adjusted to achieve 99.82 wt% benzene purity (amount of benzene / amount of benzene + C ₆ non-aromatic) in the product stream.

Example 1

Catalyst A, weight 0.10 g

Catalyst pre-treatment: (a) _{drying: under 40 sccm H 2, 50} psig , and 2 hours at 130 ℃; (b) H ₂ S treatment in succession: 40 sccm of H ₂ (with 50 ppm H ₂ S), 50 psig, and 350 ° C for 30 minutes

Hydrocarbon feed composition: 70.0 wt% Benzene, 15.0 wt% 3-methylpentane, 15.0 wt% Methylcyclopentane

The hydrocarbon feed rate varied from 20.6 to 24.7 μl / min and operated at a WHSV of 9.9 to 11.9 h ^-1 .

H ₂ (+ H ₂ S) ratio: the H2 to HC molar ratio is adjusted to maintain a 4: 1 ratio and the H ₂ S content is adjusted to 50 ppm

The catalyst bed temperature was 470 占 폚, the pressure was 200 psig

Example 2

Catalyst B, weight 0.10 g

Catalyst Pretreatment: Same as Example 1

Hydrocarbon Feed Composition and Ratio: Same as Example 1

The hydrocarbon feed rate varied from 18.5 to 22.7 μl / min and the rate of hydrocarbons from 8.9 to 10.9 h ^-1 WHSV.

H ₂ (+ H ₂ S) ratio: Change as described in Example 1

Catalyst bed temperature 470 ° C, pressure 200 psig.

Example 3

Catalyst C, weight 0.10 g

Catalyst Pretreatment: Same as Example 1

Hydrocarbon Feed Composition and Ratio: Same as Example 1

The hydrocarbon feed rate varied from 18.9 to 22.7 μl / min, and from 9.1 to 10.9 h ^-1 WHSV.

H ₂ (+ H ₂ S) ratio: Change as described in Example 1

Catalyst bed temperature 470 ° C, pressure 200 psig.

Example 4

Catalyst D, weight 0.10 g

Catalyst Pretreatment: Same as Example 1

Hydrocarbon Feed Composition and Ratio: Same as Example 1

The hydrocarbon feed rate varied from 18.9 to 22.7 μl / min, and from 9.1 to 10.9 h ^-1 WHSV.

H ₂ (+ H ₂ S) ratio: Change as described in Example 1

Catalyst bed temperature 470 ° C, pressure 200 psig.

[Effects on the catalytic performance of the production method] Example catalyst Pt
(wt%) Benzene purity WHSV
(h ^-1 ) Content in wastewater (wt%) benzene methane reshuffle
Hydrocarbon ¹ gun
Aromatic One A 0.066 99.82 11.16 60.89 1.21 34.15 65.74 2 B 0.0808 99.82 9.06 62.11 1.24 33.16 66.68 3 C 0.0758 99.82 9.72 59.89 1.13 35.79 64.10 4 D 0.0711 99.82 9.68 60.06 1.19 35.19 64.68

¹ light hydrocarbons = C ₁ -C ₅ hydrocarbons

It can be seen that the catalysts (B, C, D) prepared according to the present invention exhibit catalytic performance comparable to the catalyst (A) produced by the time consuming method.

Described below are some embodiments of the methods disclosed herein.

Embodiment 1: (i) providing a molded article comprising a zeolite and a binder, wherein the zeolite is ZSM-5 wherein the molar ratio of silica (SiO ₂ ) to alumina (Al ₂ O ₃ ) is 25 to 75, Is obtained by molding, firing and cooling; (ii) optionally drying the shaped body at a temperature of 100 to 300 DEG C for at least 1 hour; (iii) depositing a metal hydride on the shaped body by impregnation for a period of not more than 2 hours such that the amount of the metal hydride is from 0.010 to 0.30 wt% based on the total catalyst; (iv) optionally rinsing the metal deposited body with water; And (v) heat-treating the metal-deposited formed article in air at a temperature of 250 to 300 ° C for 1 to 5 hours, wherein the catalyst is present in an amount of 0.05 weight% % ≪ / RTI > of sodium and cesium.

Embodiment 2: The method according to Embodiment 1, wherein the step (ii) is not included.

Embodiment 3: A method according to any one of the preceding embodiments, wherein the method does not comprise (iv).

Embodiment 4: The method according to any one of the preceding embodiments, wherein step (v) is carried out at a temperature of 270 to 290 ° C for 1 to 3 hours.

Embodiment 5: In the method according to any of the preceding embodiments, the catalyst comprises less than 0.05% by weight total of alkali and alkaline earth metals, preferably less than 0.04% by weight, based on the total weight of the catalyst, or Methods comprising less than 0.01% by weight

Embodiment 6: The embodiment in the method according to aspect 1, wherein the zeolite has a silica (SiO ₂₎ to alumina (Al ₂ O ₃₎ molar ratio is from 30 to 65, preferably 35 to 60, more preferably from 40 to 55 of How to be

Embodiment 7: The method according to any one of the preceding embodiments, wherein the content of hydrogenated metal is 0.015 to 0.095 wt%, preferably 0.035 to 0.080 wt%, or 0.040 to 0.075 wt% Way.

Embodiment 8: The method according to any one of the preceding embodiments, wherein said hydrogenated metal is platinum.

Embodiment 9: In the process according to any of the preceding embodiments, the hydrocracking catalyst comprises 0.01 parts by weight of bismuth (based on 100 parts by weight of the catalyst), preferably less than 0.01 part by weight of tin, 0.02 parts by weight Less lead, less than 0.01 parts by weight of bismuth, and less than 0.01 parts by weight of molybdenum.

Embodiment 10: The method according to any one of the preceding embodiments, wherein the content of the binder in the hydrocracking catalyst is from 10 to 50% by weight, based on the total catalyst.

Embodiment 11: The method according to any one of the preceding embodiments, wherein said hydrocracking catalyst is an extrudate having an average diameter of from 0.1 to 15 mm.

Embodiment 12: The method according to any one of the preceding embodiments, wherein the catalyst comprises less than 0.04% by weight sodium and cesium, or less than 0.01% by weight based on the weight of the overall catalyst.

Embodiment 13: A method according to any one of the preceding embodiments, wherein no alkali or alkaline earth metal is added to the zeolite.

Embodiment 14: The method according to any one of the preceding embodiments, wherein the zeolite is in a hydrogen form.

Embodiment 15: The method according to any one of the preceding embodiments, wherein said zeolite is not base exchanged.

Embodiment 16: The method according to any one of the preceding embodiments, wherein the zeolite is not ion-exchanged with any metal of group IA or IIA on the periodic table.

Embodiment 17: (a) providing a hydrocracked feed stream comprising C ₅ -C ₁₂ hydrocarbons; (b) process comprising the hydrocracking feed stream temperature of 300 to a gauge pressure, and WHSV of from 3 to 30 h ^-1 of 5000 kPa for 425 to 580 ℃ for producing a hydrogenolysis product stream comprising BTX Contacting the hydrocracking catalyst formed by any one of the preceding embodiments with hydrogen in the presence of hydrogen; And (c) separating the BTX from the hydrocracked product stream.

Embodiment 18: In the process according to Embodiment 17, the hydrocracked feed stream is passed through a first stage or multi-stage hydrogen-treated heat gasoline, direct naphtha, hydrocracked gasoline, light coker naphtha and coke oven, FCC gasoline A reformate or a mixture thereof and comprising a fresh feed stream which is subjected to hydrogenation, mono-aromatic compound concentration and / or depentanization and optionally a stream re-used from said hydrocracked product stream.

Embodiment 19: A process according to any one of embodiments 17 and 18, wherein the hydrocracked feed stream is provided by a process that does not involve removing benzene.

Embodiment 20: A process according to any one of embodiments 17 to 19, wherein said hydrocracked feed stream comprises 10 to 90% by weight of benzene.

Claims (15)

(i) providing a molded product (shaped body) containing the zeolite (zeolite) and a binder (binder), the formed body is obtained by molding and firing (calcination) and cooling, the zeolite are silica (SiO ₂₎ ZSM-5 wherein the molar ratio of alumina (Al ₂ O ₃ ) is 25-75;
(ii) optionally drying said shaped body at 100-300 占 폚 for at least 1 hour;
(iii) depositing a hydrogenation metal on the shaped body by impregnation for a period of not more than 2 hours so that the amount of the hydrogenated metal is 0.010-0.30 wt% with respect to the entire catalyst step;
(iv) optionally rinsing the shaped body on which the metal is deposited with water; And
(v) heat-treating the formed body on which the metal is deposited, at a temperature of 250-300 ° C in air for 1-5 hours;
Wherein the catalyst comprises less than 0.05 wt.%, Preferably less than 0.04 wt.%, Or less than 0.01 wt.%, Based on the total weight of the catalyst, of the total amount of sodium and cesium Wherein the hydrocracking catalyst is a hydrocracking catalyst. The method according to claim 1,
(ii). < / RTI > 6. A method according to any one of the preceding claims,
RTI ID = 0.0 > (iv). < / RTI > 6. A method according to any one of the preceding claims,
(v) is carried out at a temperature of 270-290 DEG C for 1-3 hours. 6. A method according to any one of the preceding claims,
Wherein the catalyst comprises less than 0.05 wt.%, Preferably less than 0.04 wt.%, Or less than 0.01 wt.%, Based on the weight of the total catalyst, of the total amount of alkali metal and alkaline earth metal. The method according to claim 1,
Wherein the zeolite has a molar ratio of silica (SiO ₂ ) to alumina (Al ₂ O ₃ ) of from 30 to 65, preferably from 35 to 60, more preferably from 40 to 55. 6. A method according to any one of the preceding claims,
Wherein the amount of the hydrogenated metal is 0.015-0.095 wt.%, Preferably 0.035-0.080 wt.%, Based on the total amount of the catalyst. 6. A method according to any one of the preceding claims,
Characterized in that the hydrogenated metal is platinum. 6. A method according to any one of the preceding claims,
The hydrocracking catalyst comprises 0.01 parts by weight of bismuth, preferably less than 0.01 parts by weight tin, less than 0.02 parts by weight lead, less than 0.01 part by weight (based on 100 parts by weight of the catalyst) Bismuth and less than 0.01 part by weight of molybdenum. 6. A method according to any one of the preceding claims,
Wherein the content of the binder in the hydrocracking catalyst is 10-50 wt% based on the total amount of the catalyst. 6. A method according to any one of the preceding claims,
Wherein the hydrocracking catalyst is an extrudate having an average diameter of from 0.1 to 15 nm. (a) providing a hydrocracked feed stream comprising C ₅ -C ₁₂ hydrocarbons;
(b) under process conditions including the hydrocracking feed stream in the presence of hydrogen, the temperature of 425-580 ℃, pressure and 3-30h hourly space velocity (Weight Hourly Space Velocity) of ¹ of 300-500kPa gauge Contacting the hydrocracking catalyst formed by any one of the preceding claims to produce a hydrocracked product stream comprising BTX; And
(c) separating the BTX from the hydrocracking product stream; / RTI > The method of claim 12,
The hydrocracked feed stream may comprise at least one of:
Step or multistage hydrogen-treated pyrolysis gasoline, a straight-run (not subjected to hydrogenation, enrichment and / or depentanization of mono-aromatic compounds) a fresh feed stream of naphtha, hydrogen cracked gasoline, light coker naphtha and coke oven light oil, FCC gasoline, reformate, or a mixture thereof. ; And
Optionally a stream re-used from the hydrocracked product stream. The method according to any one of claims 12-13,
Wherein the hydrocracked feed stream is provided by a process that does not involve removing benzene. The method of any one of claims 12-14,
Wherein the hydrocracked feed stream comprises 10-90 wt% benzene.